EP2832834A1 - Composition de fluide de travail pour réfrigérateur - Google Patents

Composition de fluide de travail pour réfrigérateur Download PDF

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Publication number
EP2832834A1
EP2832834A1 EP13768396.7A EP13768396A EP2832834A1 EP 2832834 A1 EP2832834 A1 EP 2832834A1 EP 13768396 A EP13768396 A EP 13768396A EP 2832834 A1 EP2832834 A1 EP 2832834A1
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EP
European Patent Office
Prior art keywords
refrigerating machine
refrigerant
less
carbon atoms
working fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP13768396.7A
Other languages
German (de)
English (en)
Other versions
EP2832834A4 (fr
Inventor
Masanori Saito
Hiroshi Eto
Tsutomu Takahashi
Kuniko ADEGAWA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JX Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Oil and Energy Corp filed Critical JX Nippon Oil and Energy Corp
Publication of EP2832834A1 publication Critical patent/EP2832834A1/fr
Publication of EP2832834A4 publication Critical patent/EP2832834A4/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/10—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M105/12—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms monohydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18—Ethers, e.g. epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • F25B1/005—Compression machines, plants or systems with non-reversible cycle of the single unit type
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/102—Alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/106—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/24—Only one single fluoro component present
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/103—Containing Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a working fluid composition for a refrigerating machine, and more specifically relates to a working fluid composition for a refrigerating machine that contains a refrigerant which contains monofluoroethane (also referred to as "HFC-161" or "R161").
  • CFC chlorofluorocarbon
  • HCFC hydrofluorocarbon
  • HFC-134a, R407C, and R410A are normally used as refrigerants for car air-conditioners, cold storage chambers, or room air-conditioner.
  • ODP ozone depletion potential
  • GWP global warming potential
  • difluoromethane has been studied as one of alternate candidates of these refrigerants, difluoromethane has the following problems: the global warming potential thereof is not sufficiently low; the boiling point thereof is so low that thermodynamic characteristics cannot be applied to a current refrigeration system directly; and difluoromethane is not easily compatible with lubricating oils (refrigerating machine oils) used for conventional HFC refrigerants, such as polyol esters and polyvinyl ethers.
  • lubricating oils refrigerating machine oils
  • a working medium including 80% by mass or more of one or more first components selected from 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoro-2-monofluoroethane (HFC-134a) and 1,1,1-trifluoro-2,2-difluoroethane (HFC-125) as first components, and 20% by mass or less of carbon dioxide (R744) as a second component has been proposed (Patent Literature 4).
  • Hydrocarbons such as isobutane (R600a) and propane (R290) that are flammable, in which the ODP is 0 and the GWP is as extremely low as about 3, have also been studied (Patent Literatures 5 to 7).
  • An object in a refrigeration/air-conditioning system is to find out a working fluid satisfying all of the following many characteristics: with respect to a refrigerant, adverse influences on the environment are small due to a low global warming potential (GWP), use with safety is possible because burning and explosion hardly occur, thermodynamics characteristics are suitable for applications, and large-scale supply is possible because the chemical structure is simple; and with respect to characteristics in the system where a refrigerant and a refrigerating machine oil coexist, they are soluble in each other (compatibility) and are excellent in stability, and an oil film that is not worn is maintained (lubricity).
  • GWP global warming potential
  • HFC-32 (GWP: 675), HFO-1234yf (GWP: 4), HFC-152a (GWP: 120), and propane (R290, GWP: 3) are studied as major candidates, as described above, but each of them is problematic.
  • thermodynamics characteristics because the boiling point of HFC-32 is -52°C and is lower than that of the current refrigerant, HCFC-22, used for room air-conditioners, all-in-one air conditioners, and the like by about 10°C, the pressure is higher at the same temperature and thus the discharge temperature is excessively increased; and furthermore, the GWP thereof is 675 and thus is not sufficiently low.
  • HFO-1234yf being an unsaturated hydrofluorocarbon, whose GWP is also extremely low
  • HFO-1234yf is compatible with the refrigerating machine oil such as polyol esters and an ether compound used for the current HFC, and thus is applicable.
  • unsaturated hydrofluorocarbons have unstable double bonds in their molecules and thus are poor in thermal/chemical stability.
  • HFO-1234yf whose boiling point is -25°C
  • HFC-134a whose boiling point is -26°C is used
  • HCFC-22 whose boiling point is -41°C and whose pressure is relatively high is used and the amount of the refrigerant used is large, because efficiency is too low.
  • HFC-152a whose GWP is also low, is a well-balanced refrigerant in terms of characteristics, but is flammable.
  • HFC-152a whose boiling point is -25°C, however, can be applied only in the field of HFC-134a due to thermodynamics characteristics thereof.
  • switching to isobutane (R600a) whose GWP is as low as 3 has already progressed.
  • Isobutane however, also has the problem of incapable of being applied to applications in which the amount of the refrigerant charged is small, in terms of thermodynamics characteristics and safety.
  • Propane whose boiling point is -42°C and whose GWP is also extremely low, is excellent in refrigerant characteristics in the field in which HCFC-22, or as an alternate thereof, R410A that is a mixed refrigerant where the ODP is 0 and HFC-32 and HFC-125 are each present in 50% by mass is used. Propane, however, is highly flammable and also high in explosibility, and has the problem of safety.
  • the present invention has been made under such circumstances, and an object thereof is to provide a working fluid composition for a refrigerating machine that has little adverse influences on the environment and that can achieve compatibility, thermal/chemical stability and lubricity in a highly effective system at high levels.
  • the present inventors have made intensive studies in order to achieve the above object, and as a result, have found that the above problems can be solved by using a refrigerant comprising monofluoroethane (HFC-161), and a refrigerating machine oil with a specific ester or ether as a base oil, leading to the completion of the present invention.
  • a refrigerant comprising monofluoroethane (HFC-161)
  • a refrigerating machine oil with a specific ester or ether as a base oil
  • the present invention provides a working fluid composition for a refrigerating machine, comprising: a refrigerant comprising monofluoroethane (HFC-161); and a refrigerating machine oil comprising at least one selected from a polyol ester, a polyvinyl ether and a polyalkylene glycol compound as a base oil, wherein a carbon/oxygen molar ratio of the base oil is 2.5 or more and 5.8 or less.
  • a refrigerant comprising monofluoroethane (HFC-161)
  • a refrigerating machine oil comprising at least one selected from a polyol ester, a polyvinyl ether and a polyalkylene glycol compound as a base oil, wherein a carbon/oxygen molar ratio of the base oil is 2.5 or more and 5.8 or less.
  • the refrigerant may also further comprise at least one selected from a compound represented by the following formula (A) and carbon dioxide.
  • A a compound represented by the following formula (A) and carbon dioxide.
  • C p H q F r (A) [p represents an integer of 1 to 4, q represents an integer of 1 to 10, and r represents an integer of 0 to 5.]
  • the refrigerant comprises the compound represented by the formula (A)
  • at least one selected from difluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, propane (R290) and isobutane (R600a) is preferable as the compound.
  • a mass ratio of the refrigerant to the refrigerating machine oil be 90 : 10 to 30 : 70.
  • a global warming potential of the refrigerant be 300 or less.
  • the base oil comprises a polyol ester whose carbon/oxygen molar ratio is 2.5 or more and 5.8 or less
  • preferable examples of the polyol ester include polyol esters obtainable by synthesis from fatty acids having 4 to 9 carbon atoms and polyhydric alcohols having 4 to 12 carbon atoms.
  • the base oil comprises a polyalkylene glycol having a carbon/oxygen molar ratio of 2.5 or more and 5.8 or less
  • preferable examples of the polyalkylene glycol compound include a compound having a homopolymerization chain of propylene oxide or a copolymerization chain of propylene oxide and ethylene oxide, at least one of both ends of the chain being blocked by an ether bond.
  • the base oil comprises a polyvinyl ether having a carbon/oxygen molar ratio of 2.5 or more and 5.8 or less
  • preferable examples of the polyvinyl ether include a polyvinyl ether having a structural unit represented by the following formula (1).
  • R 1 , R 2 and R 3 may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
  • R 4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms or an ether bond oxygen-containing divalent hydrocarbon group having 2 to 20 carbon atoms
  • R 5 represents a hydrocarbon group having 1 to 20 carbon atoms
  • m represents a number such that an average value of m in the polyvinyl ether is 0 to 10
  • R 1 to R 5 may be the same or different in each occurrence of the structural units, and when m represents 2 or more in one structural unit, a plurality of R 4 O may be the same or different.
  • a working fluid composition for a refrigerating machine that has little adverse influences on the environment and that can achieve compatibility, thermal/chemical stability and lubricity in a highly effective system at high levels is provided.
  • a working fluid composition for a refrigerating machine comprises a refrigerant comprising monofluoroethane, and a refrigerating machine oil comprising at least one selected from a polyol ester, a polyvinyl ether and a polyalkylene glycol compound as a base oil, wherein a carbon/oxygen molar ratio of the base oil is 2.5 or more and 5.8 or less.
  • the proportions of the refrigerant and the refrigerating machine oil blended are not particularly limited, but the mass ratio of the refrigerant to the refrigerating machine oil is preferably 90 : 10 to 30 : 70 and more preferably 80 : 20 to 40 : 60.
  • the refrigerant in the present embodiment contains monofluoroethane (HFC-161).
  • Monofluoroethanes have one fluorine atom in their molecules and exhibit characteristic properties.
  • propane R290
  • propane R290
  • propane R290
  • propane R290
  • Propane is highly flammable, and thus has the large problem of safety and the following problem: in the case of existing with the refrigerating machine oil, it is so dissolved in the refrigerating machine oil that the viscosity of the oil is significantly reduced, causing lubricity to be deteriorated.
  • monofluoroethanes has a low GWP, specifically 100 or less, and a boiling point of -37°C which is close to the boiling point of HCFC-22, -41°C.
  • its thermodynamics characteristics are similar to those of HCFC-22, and it is good in thermodynamics characteristics as the refrigerant, compatibility with the refrigerating machine oil, and stability, even by itself.
  • HFC-161 has an explosion lower limit of 5.0% by volume while the explosion lower limit of propane is 2.1% by volume, and HFC-161 has a boiling point higher than that of propane by 5°C, and a lower pressure than propane, which hardly causes refrigerant leakage and results in much higher safety.
  • the refrigerant concentration in a room rarely reaches 5.0% by volume.
  • monofluoroethanes have fluorine in their molecules, the amount thereof dissolved in the refrigerating machine oil is much smaller than that of propane, and therefore the amount of the refrigerant charged per refrigeration/air-conditioning apparatus is small.
  • the amount dissolved in the coexisting refrigerating machine oil is small, the reduction in viscosity of the refrigerating machine oil is also small, resulting in an advantage in lubricity; and since no double bond is present in the molecules, stability is not problematic.
  • the refrigerant in the present embodiment may also further contain at least one selected from a compound represented by the following formula (A) and carbon dioxide, in addition to the monofluoroethane.
  • A a compound represented by the following formula (A) and carbon dioxide, in addition to the monofluoroethane.
  • C p H q F r (A) [p represents an integer of 1 to 4, q represents an integer of 1 to 10, and r represents an integer of 0 to 5.]
  • the refrigerant in the present embodiment can allow the flammability resulting from the monofluoroethane to be decreased.
  • the composition of the refrigerant it is possible to easily and certainly perform adjustment of thermodynamics characteristics of the refrigerant depending on the intended use, which is effective in terms of the increase in efficiency of a system.
  • Preferable components combined with the monofluoroethane include, with listed together with the boiling point, GWP and flammability noted in parentheses, HFC-32 (-52°C, 675, low flammable), HFC-152a (-25°C, 120, flammable), HFC-143a (-47°C, 4300, low flammable), HFC-134a (-26°C, 1300, non-flammable), HFC-125 (-49°C, 3400, non-flammable), HFO-1234ze (-19°C, 6, low flammable), HFO-1234yf (-29°C, 4, low flammable), propane (-42°C, 3, highly flammable), isobutane (-12°C, 3, highly flammable), and carbon dioxide (-78°C, 1, non-flammable). These components may be used in combination of two or more.
  • a non-flammable refrigerant may be blended, but a non-flammable HFC refrigerant is generally high in GWP. Then, there is a method of blending a low flammable refrigerant for the balance of characteristics.
  • carbon dioxide is non-flammable and is the standard compound of GWP, whose GWP is as low as 1, blending thereof is effective as long as it has no influence on thermodynamics characteristics.
  • HFC-32, HFC-143a, and HFC-125 are candidates.
  • HFO-1234ze, HFO-1234yf and carbon dioxide, and further propane and isobutane are preferable.
  • the refrigerant is selected from relatively low-pressure refrigerants such as HFC-134a, HFO-1234ze and HFO-1234yf whose boiling points are higher than -30°C, in consideration of the overall balance of characteristics.
  • the proportion of the monofluoroethane contained in the mixed refrigerant is preferably 50% by mass or more and more preferably 60% by mass or more.
  • the GWP is preferably set to 300 or less, more preferably 200 or less, and further preferably 150 or less from the viewpoint of the global environment protection.
  • the mixed refrigerant for use in the present embodiment is preferably an azeotropic mixture, it is not particularly required to be an azeotropic mixture as long as it has physical properties necessary as the refrigerant.
  • the refrigerating machine oil according to the present embodiment contains at least one selected from a polyol ester, a polyvinyl ether and a polyalkylene glycol compound as a base oil, and the carbon/oxygen molar ratio of the base oil is 2.5 or more and 5.8 or less.
  • Carbon and oxygen in the base oil can be quantitatively analyzed by a common elemental analysis method. While a carbon analysis includes a thermal conductivity method after conversion into carbon dioxide by burning, and a gas chromatography method, an oxygen analysis is commonly a carbon reduction method in which carbon monoxide derived by carbon is quantitatively analyzed, and a Shutze-Schzaucher method is widely put into practical use.
  • the carbon/oxygen molar ratio of each of the components included in the mixed base oil is not particularly limited as long as the carbon/oxygen molar ratio of the mixed base oil is 2.5 or more and 5.8 or less, but it is preferable that the carbon/oxygen molar ratio of each of the polyol ester, the polyvinyl ether and the polyalkylene glycol compound be 2.5 or more and 5.8 or less. These preferable examples are described later.
  • the polyol ester is an ester obtainable by synthesis from a polyhydric alcohol and a carboxylic acid, and the carbon/oxygen molar ratio is preferably 2.5 or more and 5.8 or less, more preferably 3.2 or more and 5.0 or less, and further preferably 4.0 or more and 5.0 or less.
  • carboxylic acid fatty acids (aliphatic monocarboxylic acids), in particular saturated fatty acids are preferably used, and the number of carbon atoms thereof is preferably 4 or more and 9 or less and particularly preferably 5 or more and 9 or less.
  • the polyol ester may be a partial ester in which some of hydroxyl groups in the polyhydric alcohol remains as hydroxyl groups without being esterified, may be a complete ester in which all of hydroxyl groups are esterified, or may be a mixture of the partial ester and the complete ester; but the hydroxyl value is preferably 10 mgKOH/g or less, further preferably 5 mgKOH/g or less, and most preferably 3 mgKOH/g or less.
  • branched fatty acids having 4 to 9 carbon atoms include branched butanoic acids, branched pentanoic acids, branched hexanoic acids, branched heptanoic acids, branched octanoic acids, and branched nonanoic acids.
  • fatty acids branched at ⁇ -position and/or ⁇ -position are preferable, isobutanoic acid, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and the like are preferable, and among them, 2-ethylhexanoic acid and/or 3,5,5-trimethylhexanoic acid is most preferable.
  • fatty acids other than branched fatty acids having 4 to 9 carbon atoms may be included.
  • the proportion of straight fatty acids of fatty acids is preferably 50 to 95% by mol, particularly preferably 60 to 90% by mol, and further preferably 70 to 85% by mol in view of high compatibility with the refrigerating machine oil.
  • straight fatty acids having 4 to 9 carbon atoms include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid.
  • pentanoic acid and/or heptanoic acid is preferable, and in particular a mixed acid thereof is most preferable.
  • the content of straight pentanoic acid is preferably 30% by mol or more in particular in terms of compatibility, and on the other hand, is preferably 50% by mol or less and particularly preferably 45% by mol or less in particular in terms of hydrolytic stability.
  • the content of heptanoic acid is preferably 20% by mol or more, particularly preferably 25% by mol or more, and further preferably 30% by mol or more, in terms of lubricity. On the other hand, the content is 50% by mol or less and preferably 45% by mol or less in particular in terms of hydrolytic stability.
  • branched fatty acids other than straight fatty acids branched fatty acids having 5 to 9 carbon atoms, in particular, 2-ethylhexanoic acid and/or 3,5,5-trimethylhexanoic acid is preferable.
  • the content of 3,5,5-trimethylhexanoic acid is preferably 5% by mol or more and particularly preferably 10% by mol or more in particular in terms of hydrolytic stability, and on the other hand, the content is preferably 30% by mol or less and particularly preferably 25% by mol or less in particular in terms of compatibility and lubricity.
  • a mixed acid of straight pentanoic acid, straight heptanoic acid and 3,5,5-trimethylhexanoic acid is preferable, and this mixed acid is more preferably one containing 30 to 50% by mol of straight pentanoic acid, 20 to 50% by mol of straight heptanoic acid and 5 to 30% by mol of 3,5,5-trimethylhexanoic acid.
  • polyhydric alcohols having 2 to 6 hydroxyl groups are preferably used as the polyhydric alcohol forming the polyol ester.
  • the number of carbon atoms of polyhydric alcohols is preferably 4 to 12 and particularly preferably 5 to 10.
  • Hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol and di-(pentaerythritol) are preferable. Since being particularly excellent in compatibility with the refrigerant and in hydrolytic stability, pentaerythritol or a mixed ester of pentaerythritol and di-(pentaerythritol) is most preferable.
  • the carbon/oxygen molar ratio of the polyvinyl ether is preferably 2.5 or more and 5.8 or less, more preferably 3.2 or more and 5.8 or less, and further preferably 4.0 or more and 5.0 or less. If the carbon/oxygen molar ratio is less than this range, hygroscopicity is higher, and if the ratio is more than this range, compatibility is deteriorated.
  • the weight average molecular weight of the polyvinyl ether is preferably 200 or more and 3000 or less and more preferably 500 or more and 1500 or less.
  • the polyvinyl ether preferably used in the present embodiment has a structural unit represented by the following formula (1): [R 1 , R 2 and R 3 may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 represents a divalent hydrocarbon group having 1 to 10 carbon atoms or an ether bond oxygen-containing divalent hydrocarbon group having 2 to 20 carbon atoms, R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, m represents a number such that an average value of m in the polyvinyl ether is 0 to 10, R 1 to R 5 may be the same or different in each occurrence of the structural units, and when m represents 2 or more in one structural unit, a plurality of R 4 O may be the same or different.]
  • At least one of R 1 , R 2 and R 3 in the above formula (1) is preferably a hydrogen atom, and all thereof are particularly preferably a hydrogen atom.
  • m in the formula (1) is preferably 0 or more and 10 or less, particularly preferably 0 or more and 5 or less, and further preferably 0.
  • R 5 in the formula (1) represents a hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group includes an alkyl group, a cycloalkyl group, a phenyl group, an aryl group, an arylalkyl group, and an alkyl group, and in particular an alkyl group having 1 to 5 carbon atoms is preferable.
  • the polyvinyl ether according to the present embodiment may be a homopolymer constituted by one type of the structural unit represented by the formula (1) or a copolymer constituted by 2 or more type of the structural units, but the copolymer brings about the effect of further enhancing lubricity, insulation property, hygroscopicity, and the like while satisfying compatibility.
  • the types of monomers serving as raw materials, the type of an initiator, and the rate of a copolymer can be selected to thereby adapt the performances of an oil agent to the intended levels.
  • an oil agent can be obtained at will according to requirements such as lubricity and compatibility that vary depending on the type of a compressor in a refrigeration system or an air-conditioning system, the material of a lubrication portion, refrigeration ability, the type of a refrigerant, and the like.
  • the copolymer may be any of a block copolymer and a random copolymer.
  • the polyvinyl ether according to the present embodiment is a copolymer
  • the copolymer include a structural unit (1-1) represented by the above formula (1) wherein R 5 represents an alkyl group having 1 to 3 carbon atoms, and a structural unit (1-2) represented by the above formula (1) wherein R 5 represents an alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, further preferably 3 to 8 carbon atoms.
  • R 5 in the structural unit (1-1) is particularly preferably an ethyl group
  • R 5 in the structural unit (1-2) is particularly preferably an isobutyl group.
  • the molar ratio of the structural unit (1-1) to the structural unit (1-2) is preferably 5 : 95 to 95 : 5, more preferably 20 : 80 to 90 : 10, and further preferably 70 : 30 to 90 : 10. In the case where the molar ratio departs from the above range, there is a tendency toward insufficient compatibility with the refrigerant and higher hygroscopicity.
  • the polyvinyl ether according to the present embodiment may be one constituted by only the structural unit represented by the above formula (1), but may be a copolymer further including a structural unit represented by the following formula (2).
  • the copolymer may be any of a block copolymer and a random copolymer.
  • R 6 to R 9 may be the same as or different from one another and each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the polyvinyl ether according to the present embodiment can be produced by polymerization of each corresponding vinyl ether-based monomer, and copolymerization of a corresponding hydrocarbon monomer having an olefinic double bond with a corresponding vinyl ether-based monomer.
  • a monomer represented by the following formula (3) is suitable.
  • [R 1 , R 2 , R 3 , R 4 , R 5 and m represent the same meaning as in R 1 , R 2 , R 3 , R 4 , R 5 and m in the formula (1), respectively.
  • ethers having the following end structures are suitable.
  • polyvinyl ether-based compounds in particular the following is suitable as a main component of the refrigerating machine oil according to the present embodiment.
  • the polyvinyl ether according to the present embodiment can be produced by subjecting the above monomer to radical polymerization, cation polymerization, radiation polymerization, or the like. After completion of the polymerization reaction, a usual separation/purification method is if necessary conducted, and thus the intended polyvinyl ether-based compound having the structural unit represented by the formula (1) is obtained.
  • the carbon/oxygen molar ratio is in the predetermined range, and the carbon/oxygen molar ratio of a raw material monomer can be regulated to thereby produce a polymer whose molar ratio is in the above range. That is, when the rate of a monomer whose carbon/oxygen molar ratio is high is high, a polymer whose carbon/oxygen molar ratio is high is obtained, and when the rate of a monomer whose carbon/oxygen molar ratio is low is high, a polymer whose carbon/oxygen molar ratio is low is obtained.
  • a polymer whose carbon/oxygen molar ratio is higher than the carbon/oxygen molar ratio of the vinyl ether-based monomer is obtained, but the proportion thereof can be regulated by the rate and the number of carbon atoms of the hydrocarbon monomer having an olefinic double bond to be used.
  • a side reaction may be caused and thus an unsaturated group such as an aryl group may be formed in the molecule.
  • an unsaturated group such as an aryl group may be formed in the molecule.
  • the following phenomenon easily occurs: the thermal stability of the polyvinyl ether itself is deteriorated, a polymerized produce is generated to generate sludge, or antioxidative property (oxidation preventing property) is deteriorated to generate peroxide.
  • peroxide is generated, it is decomposed to generate a compound having a carbonyl group, and the compound having a carbonyl group further generates sludge to easily cause blockage of a capillary.
  • the degree of unsaturation is preferably 0.04 meq/g or less, more preferably 0.03 meq/g or less, and most preferably 0.02 meq/g or less.
  • the peroxide value is preferably 10.0 meq/kg or less, more preferably 5.0 meq/kg or less, and most preferably 1.0 meq/kg.
  • the carbonyl value is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and most preferably 20 ppm by weight or less.
  • the degree of unsaturation, the peroxide value and the carbonyl value in the present invention are each the value measured by the Standard Methods for the Analysis of Fats, Oils and Related Materials, established by the Japan Oil Chemists' Society. That is, the degree of unsaturation in the present invention is the value (meq/g) obtained by reacting a Wijs solution (ICl-acetic acid solution) with a sample, leaving the resultant to stand in a dark area, thereafter reducing the excess ICl to iodine, titrating the iodine content with sodium thiosulfate to calculate the iodine value, and converting the iodine value to the vinyl equivalent; the peroxide value in the present invention is the value (meq/kg) obtained by adding potassium iodide to a sample, titrating the free iodine generated with sodium thiosulfate, and converting the free iodine to the number of milliequivalents with
  • the carbon/oxygen molar ratio of the polyalkylene glycol (PAG) compound according to the present embodiment is preferably 2.5 or more and 5.8 or less, preferably 2.5 or more and 4.0 or less, and further preferably 2.7 or more and 3.5 or less. If the molar ratio is less than this range, hygroscopicity is high and electrical insulation property is deteriorated, and if the molar ratio is more than this range, compatibility is deteriorated.
  • the weight average molecular weight of the polyalkylene glycol compound is preferably 200 or more and 3000 or less, and more preferably 500 or more and 1500 or less.
  • Polyalkylene glycols include those of various chemical structures, but a basic compound thereof is polyethylene glycol, polypropylene glycol, polybutylene glycol, or the like.
  • the unit structure thereof is oxyethylene, oxypropylene, or oxybutylene, and polyalkylene glycols can be obtained by subjecting each monomer, ethylene oxide, propylene oxide, or butylene oxide, as a raw material, to ring-opening polymerization.
  • Examples of the polyalkylene glycol include a compound represented by the following formula (9): R 101 -[(OR 102 ) f -OR 103 ] g (9)
  • R 101 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms or a residue of a compound having 2 to 8 hydroxyl groups
  • R 102 represents an alkylene group having 2 to 4 carbon atoms
  • R 103 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms
  • f represents an integer of 1 to 80
  • g represents an integer of 1 to 8.
  • the alkyl group represented by each of R 101 and R 103 may be any of straight, branched and cyclic alkyl groups.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10 and more preferably 1 to 6. If the number of carbon atoms of the alkyl group is more than 10, compatibility with a working medium tends to be deteriorated.
  • alkyl group portion of the acyl group represented by each of R 101 and R 103 may be any of straight, branched and cyclic alkyl group portions.
  • the number of carbon atoms of the acyl group is preferably 2 to 10 and more preferably 2 to 6. If the number of carbon atoms of the acyl group is more than 10, compatibility with a working medium may be deteriorated to cause phase separation.
  • R 101 and R 103 are alkyl groups or acyl groups
  • the groups represented by R 101 and R 103 may be the same or different.
  • g represents 2 or more
  • a plurality of R 101 and R 103 in the same molecule may be the same or different.
  • this compound may be a chain group or may be a cyclic group.
  • At least one of R 101 and R 103 is preferably an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms) and particularly preferably a methyl group in terms of compatibility with a working medium.
  • both of R 101 and R 103 are preferably an alkyl group (more preferably alkyl groups having 1 to 4 carbon atoms) and particularly preferably a methyl group in terms of thermal/chemical stability.
  • any one of R 101 and R 103 is an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms) and other thereof is a hydrogen atom, and particularly preferably, one is a methyl group and other is a hydrogen atom, in terms of easiness of production and cost.
  • both of R 101 and R 103 are preferably a hydrogen atom in terms of lubricity and solubility of sludge.
  • R 102 in the above formula (9) represents an alkylene group having 2 to 4 carbon atoms, and specific examples of such an alkylene group include an ethylene group, a propylene group, and a butylene group.
  • an oxyalkylene group as a repeating unit represented by OR 102 includes an oxyethylene group, an oxypropylene group, and an oxybutylene group. Oxyalkylene groups in the same molecule may be the same, and 2 or more oxyalkylene groups may be included.
  • a copolymer including an oxyethylene group (EO) and an oxypropylene group (PO) is preferable from the viewpoints of compatibility with a working medium and viscosity-temperature characteristics, and in this case, the proportion (EO/(PO+EO)) of the oxyethylene group in the sum of the oxyethylene group and the oxypropylene group is preferably in a range from 0.1 to 0.8 and more preferably in a range from 0.3 to 0.6 in terms of baking load and viscosity-temperature characteristics.
  • the value of EO/(PO+EO) is preferably in a range from 0 to 0.5, more preferably in a range from 0 to 0.2, and most preferably 0 (namely, propylene oxide homopolymer), in terms of hygroscopicity and thermal and oxidation stability.
  • f represents the number of repetitions of the oxyalkylene group OR 102 (degree of polymerization), and represents an integer of 1 to 80.
  • g represents an integer of 1 to 8.
  • R 101 represents an alkyl group or an acyl group
  • g represents 1.
  • R 101 represents a residue of a compound having 2 to 8 hydroxyl groups
  • g represents the number of hydroxyl groups in the compound.
  • the product (f ⁇ g) of f and g is not particularly limited, but it is preferable that the average value of f ⁇ g be 6 to 80 in order to satisfy the above-described requirements and performances as the lubricating oil for a refrigerating machine in a well-balanced manner.
  • the number average molecular weight of the polyalkylene glycol represented by the formula (9) is preferably 500 to 3000, further preferably 600 to 2000 and more preferably 600 to 1500, and it is preferable that f represent a number so that the number average molecular weight of the polyalkylene glycol satisfies the above conditions. In the case where the number average molecular weight of the polyalkylene glycol is too low, lubricity under coexistence with the refrigerant is insufficient.
  • the hydroxyl value of the polyalkylene glycol is not particularly limited, but it is desirable that the hydroxyl value be 100 mgKOH/g or less, preferably 50 mgKOH/g or less, further preferably 30 mgKOH/g or less, and most preferably 10 mgKOH/g or less.
  • the polyalkylene glycol according to the present embodiment can be synthesized using a conventionally known method ("Alkylene Oxide Polymers", Shibata, M. et al., Kaibundo, issued on November 20, 1990).
  • the polyalkylene glycol represented by the above formula (9) is obtained by performing addition polymerization of one or more predetermined alkylene oxides to an alcohol (R 101 OH; R 101 represents the same meaning as in R 101 in the above formula (9)), and subjecting the hydroxyl group at the end to etherification or esterification.
  • the resulting polyalkylene glycol may be any of a random copolymer and a block copolymer, but it is preferably a block copolymer because of tending to be more excellent in oxidation stability and lubricity, and preferably a random copolymer because of tending to be more excellent in low-temperature fluidity.
  • the kinematic viscosity at 100°C of the polyalkylene glycol according to the present embodiment is preferably 5 to 20 mm 2 /s, preferably 6 to 18 mm 2 /s, more preferably 7 to 16 mm 2 /s, further preferably 8 to 15 mm 2 /s, and most preferably 10 to 15 mm 2 /s.
  • the kinematic viscosity at 100°C is less than the above lower limit, lubricity under coexistence with the refrigerant is insufficient, and on the other hand, if the kinematic viscosity at 100°C is more than the above upper limit, a composition range in which compatibility with the refrigerant is exhibited is narrow, and lubrication failure in a refrigerant compressor and inhibition of heat exchange in an evaporator easily occur.
  • the kinematic viscosity at 40°C of the polyalkylene glycol is preferably 10 to 200 mm 2 /s and more preferably 20 to 150 mm 2 /s.
  • kinematic viscosity at 40°C is less than 10 mm 2 /s, lubricity and sealability of a compressor tend to be deteriorated, and if the kinematic viscosity at 40°C is more than 200 mm 2 /s, a composition range in which compatibility with the refrigerant is exhibited under low temperature conditions tends to be narrow, and lubrication failure in a refrigerant compressor and inhibition of heat exchange in an evaporator tend to easily occur.
  • the pour point of the polyalkylene glycol represented by the above formula (9) is preferably -10°C or lower and more preferably -20 to -50°C. If a polyalkylene glycol having a pour point of -10°C or higher is used, the refrigerating machine oil tends to be solidified at a low temperature in the refrigerant circulation system.
  • alkylene oxides such as propylene oxide may cause a side reaction and thus an unsaturated group such as an aryl group may be formed in the molecule.
  • an unsaturated group is formed in the polyalkylene glycol molecule, the following phenomenon easily occurs: the thermal stability of the polyalkylene glycol itself is deteriorated, a polymerized produce is generated to generate sludge, or antioxidative property (oxidation prevention property) is deteriorated to generate peroxide.
  • peroxide is generated, it is decomposed to generate a compound having a carbonyl group, and the compound having a carbonyl group further generates sludge to easily cause blockage of a capillary.
  • the degree of unsaturation due to an unsaturated group and the like is low, and specifically, the degree of unsaturation is preferably 0.04 meq/g or less, more preferably 0.03 meq/g or less, and most preferably 0.02 meq/g or less.
  • the peroxide value is preferably 10.0 meq/kg or less, more preferably 5.0 meq/kg or less, and most preferably 1.0 meq/kg.
  • the carbonyl value is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and most preferably 20 ppm by weight or less.
  • the reaction temperature at which propylene oxide is reacted be 120°C or lower (more preferably 110°C or lower).
  • an alkali catalyst is used during the production, an inorganic adsorbent such as activated carbon, activated white earth, bentonite, dolomite, or aluminosilicate can be used for removing the catalyst, to thereby reduce the degree of unsaturation.
  • an inorganic adsorbent such as activated carbon, activated white earth, bentonite, dolomite, or aluminosilicate can be used for removing the catalyst, to thereby reduce the degree of unsaturation.
  • the carbon/oxygen molar ratio is in a predetermined range
  • a polymer whose molar ratio is in the above range can be produced by selecting and regulating the types and the mixing ratio of the raw material monomers.
  • the content of the polyol ester, the polyvinyl ether or the polyalkylene glycol compound in the refrigerating machine oil is preferably 80% by mass or more and particularly preferably 90% by mass or more in total based on the total amount of the refrigerating machine oil in order that the refrigerating machine oil is excellent in characteristics demanded, such as lubricity, compatibility, thermal/chemical stability, and electrical insulation property.
  • a mineral oil a hydrocarbon-based oil such as an olefin polymer, a naphthalene compound and alkylbenzenes
  • an oxygen-containing synthetic oil such as carbonates, ketones, polyphenyl ethers, silicones, polysiloxanes and perfluoroethers
  • carbonates or ketones are preferably used.
  • the kinematic viscosity of the refrigerating machine oil is not particularly limited, but the kinematic viscosity at 40°C can be preferably set to 3 to 1000 mm 2 /s, more preferably 4 to 500 mm 2 /s, and most preferably 5 to 400 mm 2 /s.
  • the kinematic viscosity at 100°C can be preferably set to 1 to 100 mm 2 /s and more preferably 2 to 50 mm 2 /s.
  • the volume resistivity of the refrigerating machine oil is not particularly limited, but it can be preferably set to 1.0 ⁇ 10 9 ⁇ m or more, more preferably 1.0 ⁇ 10 10 ⁇ m or more, and most preferably 1.0 ⁇ 10 11 ⁇ m or more.
  • the volume resistivity means the value at 25°C measured according to JIS C 2101 "Electrical Insulation Oil Test Method".
  • the moisture content of the refrigerating machine oil is not particularly limited, but it can be preferably set to 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerating machine oil.
  • the moisture content is demanded to be low from the viewpoint of the influence on thermal/chemical stability and the electrical insulation property of the refrigerating machine oil.
  • the acid value of the refrigerating machine oil is not particularly limited, but it can be preferably set to 0.1 mgKOH/g or less and more preferably 0.05 mgKOH/g or less in order to prevent corrosion of a metal used for a refrigerating machine or a pipe, and to prevent decomposition of the ester contained in the refrigerating machine oil according to the present embodiment.
  • the acid value means the acid value measured according to JIS K2501 "Petroleum Products And Lubricating Oils-Neutralization Value Test Method".
  • the ash content of the refrigerating machine oil is not particularly limited, but it can be preferably set to 100 ppm or less and more preferably 50 ppm or less in order to increase the thermal/chemical stability of the refrigerating machine oil according to the present embodiment and to suppress the occurrence of sludge or the like.
  • the ash content means the value of the ash content measured according to JIS K2272 "Crude Oil/Petroleum Product Ash Content and Sulfated Ash Content Test Method".
  • the working fluid composition for a refrigerating machine can also be used in the form of being blended with various additives, if necessary. While the content of the additives is shown based on the total amount of a refrigerating machine oil composition, the content of these components in the fluid composition for a refrigerating machine is preferably 5% by mass or less and particularly preferably 2% by mass or less based on the total amount of a refrigerating machine oil composition.
  • phosphorus compound selected from the group consisting of phosphates, acidic phosphates, thiophosphates, amine salts of acidic phosphates, chlorinated phosphates, and phosphites.
  • phosphorus compounds are esters of phosphoric acid or phosphorous acid and an alkanol or a polyether type alcohol, or derivatives thereof.
  • the working fluid composition for a refrigerating machine can contain at least one epoxy compound selected from a phenylglycidylether type epoxy compound, an alkylglycidylether type epoxy compound, a glycidylester type epoxy compound, an allyloxysilane compound, an alkyloxysilane compound, an alicyclic epoxy compound, an epoxidated fatty acid monoester and an epoxidated vegetable oil in order to further improve the thermal/chemical stability thereof.
  • a phenylglycidylether type epoxy compound an alkylglycidylether type epoxy compound, a glycidylester type epoxy compound, an allyloxysilane compound, an alkyloxysilane compound, an alicyclic epoxy compound, an epoxidated fatty acid monoester and an epoxidated vegetable oil in order to further improve the thermal/chemical stability thereof.
  • the working fluid composition for a refrigerating machine can if necessary contain conventionally known additives for a refrigerating machine oil in order to further enhance the performances thereof.
  • additives includes a phenol-based antioxidant such as di-tert-butyl-p-cresol and bisphenol A, an amine-based antioxidant such as phenyl- ⁇ -naphthylamine and N,N-di(2-naphthyl)-p-phenylenediamine, a wear inhibitor such as zinc dithiophosphate, an extreme pressure agent such as chlorinated paraffins and a sulfur compound, an oilness agent such as fatty acids, a defoaming agent such as silicones, a metal deactivator such as benzotriazole, a viscosity index improver, a pour point depressant, and a detergent dispersant.
  • phenol-based antioxidant such as di-tert-butyl-p-cresol and bisphenol A
  • an amine-based antioxidant such as phen
  • the working fluid composition for a refrigerating machine according to the present embodiment is preferably used for a room air-conditioner and a cold storage chamber having a closed type reciprocating or rotating compressor, or an open-type or closed type car air-conditioner.
  • the working fluid composition for a refrigerating machine and the refrigerating machine oil according to the present embodiment are preferably used for a cooling apparatus or the like of a dehumidifier, a water heater, a refrigerator, a refrigeration and cooling warehouse, a vending machine, a showcase, a chemical plant, or the like.
  • the working fluid composition for a refrigerating machine and the refrigerating machine oil according to the present embodiment are also preferably used for one having a centrifugal compressor.
  • Base oil 1 ester of mixed fatty acid of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 50/50) with pentaerythritol. Carbon/oxygen molar ratio: 4.8
  • Base oil 2 ester of mixed fatty acid of n-pentanoic acid, n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 40/40/20) with pentaerythritol.
  • Base oil 4 compound in which both ends of polypropylene glycol were methyl-etherified. Weight average molecular weight: 1100; carbon/oxygen molar ratio: 2.9
  • Base oil 5 compound being copolymer of polyoxyethylene glycol and polyoxypropylene glycol, wherein one end was methyl-etherified.
  • HFC-161 itself, or a mixed refrigerant A, B or C in which HFC-161 was blended with HFC-134a, HFC-32, HFO-1234yf, and carbon dioxide (R744), which were neither highly flammable nor flammable and in which the GWP was relatively low, in consideration of the overall characteristics so that the GWP was 300 or less was used in each of Examples.
  • the value defined with respect to the GWP of HFC-161 was not released, and thus the maximum value, 100, was used for calculation.
  • the present invention provides a working fluid composition for use in a refrigerating machine/air-conditioner using a refrigerant containing HFC-161, and the composition can be used as a working fluid in a in a high-cooling efficiency refrigeration system having a compressor, a condenser, a throttle device, an evaporator, and the like among which the refrigerant is circulated, in particular, in a refrigerating machine/air-conditioner having a compressor such as a rotary-type, swing-type, scrolling-type, or reciprocating-type compressor, and can be suitably used in the fields of a room air-conditioner, an all-in-one air conditioner, an industrial refrigerating machine, a coolerator, a car air-conditioner, and the like.
  • a high-cooling efficiency refrigeration system having a compressor, a condenser, a throttle device, an evaporator, and the like among which the refrigerant is circulated, in particular, in a refrigerating machine
EP13768396.7A 2012-03-29 2013-03-28 Composition de fluide de travail pour réfrigérateur Ceased EP2832834A4 (fr)

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JP2012076301A JP5871688B2 (ja) 2012-03-29 2012-03-29 冷凍機用作動流体組成物
PCT/JP2013/059309 WO2013147045A1 (fr) 2012-03-29 2013-03-28 Composition de fluide de travail pour réfrigérateur

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EP2832834A4 EP2832834A4 (fr) 2015-04-22

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EP (1) EP2832834A4 (fr)
JP (1) JP5871688B2 (fr)
KR (1) KR101879567B1 (fr)
CN (1) CN104169405B (fr)
IN (1) IN2014DN07563A (fr)
WO (1) WO2013147045A1 (fr)

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CN111423852B (zh) * 2020-03-30 2021-06-29 珠海格力电器股份有限公司 三元制冷组合物及包含其的制冷装置
CN113845882B (zh) * 2021-10-21 2023-06-16 珠海格力电器股份有限公司 三元环保混合制冷剂、其制备方法及制冷系统

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JP2013203953A (ja) 2013-10-07
KR20140142265A (ko) 2014-12-11
CN104169405B (zh) 2017-10-27
KR101879567B1 (ko) 2018-07-19
CN104169405A (zh) 2014-11-26
EP2832834A4 (fr) 2015-04-22
WO2013147045A1 (fr) 2013-10-03
JP5871688B2 (ja) 2016-03-01
IN2014DN07563A (fr) 2015-04-24
US20150041705A1 (en) 2015-02-12

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